原位溶剂热聚合法制备金属有机骨架/碳化氮纳米片涂覆的固相微萃取纤维用于红茶中农药残留的高灵敏检测

doi:10.3724/SP.J.1123.2019.10036

摘要/Abstract

摘要：

有机氯（OCPs）和拟除虫菊酯（PYs）是两类广泛使用的农药，对自然环境和人类健康具有极大危害。在本研究中，通过原位溶剂热聚合法制备了金属有机骨架/碳化氮纳米片（UiO-66/HOCN）复合材料涂覆的固相微萃取（SPME）纤维，该纤维拥有良好的稳定性，并对OCPs和PYs具有高效的萃取性能。将其与气相色谱-质谱（GC-MS）相结合，建立了用于OCPs和PYs检测的高灵敏分析方法。该方法对9种农药目标物表现出了令人满意的回收率和重现性，具有检出限低（0.03~0.30 ng/L）、线性范围宽（0.1~800.0 ng/L）和线性相关系数良好（≥ 0.9978）等优点。将所建立的方法用于实际红茶样品中农药残留的检测，成功地在实际样品中检测出了艾试剂（6.6 ng/L）、α-硫丹（54.7 ng/L）和联苯菊酯（185.8 ng/L）。实验结果表明，所建立的分析方法适用于复杂基质中农药残留的分析和监测。

关键词: 多孔碳化氮纳米片, 金属骨架有机材料, 固相微萃取, 气相色谱-质谱联用, 农药, 红茶

Abstract:

Pyrethroids (PYs) and organochlorine pesticides (OCPs) are widely used to control pests and diseases in plants; however, they threaten human health. In this study, a metal-organic framework/carbon-nitrogen nanosheet composite nanomaterial (UiO-66/HOCN)-coated solid-phase microextraction (SPME) fiber was prepared by in-situ thermal polymerization. The prepared UiO-66/HOCN composite material was characterized by transmission electron microscopy, X-ray diffraction, nitrogen adsorption porosimetry, thermogravimetric analysis, and zeta potentiometry. The prepared UiO-66/HOCN composite-coated MSPE fiber was used for the enrichment and separation of OCPs and PYs, which showed good thermal and chemical stability as well as high extraction efficiency. Combined with gas chromatography-mass spectrometry (GC-MS), an efficient and sensitive method for the detection of trace levels of OCPs and PYs was developed. Under the optimal experimental conditions, wide linear ranges (0.1-800.0 ng/L), good linearity (≥ 0.9978), low limits of detection (0.03-0.30 ng/L), and acceptable repeatability (RSD ≤ 8.9%, n=3) were obtained. Typical black tea samples were analyzed by the developed method, and trace levels of aldrin (6.6 ng/g), α -endosulfan (54.7 ng/g), and bifenthrin (185.8 ng/g) were detected. The results demonstrate that the developed method has immense potential for the detection of pesticides in a complicated matrix.

Key words: porous carbon-nitrogen nanosheet, metal-organic framework (MOF), solid-phase microextraction (SPME), gas chromatography-mass spectrometry (GC-MS), pesticides, black tea

张文敏, 冯遵梅, 黄川辉, 高佳, 张兰. 原位溶剂热聚合法制备金属有机骨架/碳化氮纳米片涂覆的固相微萃取纤维用于红茶中农药残留的高灵敏检测[J]. 色谱, 2020, 38(3): 332-340.

ZHANG Wenmin, FENG Zunmei, HUANG Chuanhui, GAO Jia, ZHANG Lan. In-situ solvothermal polymerization of metal-organic framework/carbon-nitrogen nanosheet-coated solid-phase microextraction fiber for highly sensitive detection of pesticide residues in black tea[J]. Chinese Journal of Chromatography, 2020, 38(3): 332-340.

图/表 10

表1 9种农药的保留时间、定量离子及定性离子

Table 1 Retention times, quantitative ions and qualitative ions for the nine pesticides

Compound	Retention time/min	Quantitative ion (m/z)	Qualitative ions (m/z)
Heptachlor (七氯)	13.92	272	273, 272, 237
Aldrin (艾试剂)	14.82	263	263, 255, 220
Heptachlor epoxide	15.98	263	353, 263, 193
(环氧七氯)
α-Chlordane (α-氯丹)	17.01	373	375, 373, 272
p, p′-DDE (p, p′-滴滴伊)	17.63	318	318, 246, 176
α-Endosulfan (α-硫丹)	18.64	241	241, 206, 195
p, p′-DDD (p, p′-滴滴滴)	18.92	235	235, 200, 165
p, p′-DDT (p, p′-滴滴涕)	20.10	235	235, 200, 165
Bifenthrin (联苯菊酯)	21.91	181	386, 241, 181

图1 UiO-66/HOCN复合材料中不同HOCN掺杂比例对9种农药的萃取性能(n=3)

Fig. 1 Extraction performance of UiO-66/HOCN composite materials with various contents of HOCN for the nine pesticides (n=3) Experimental conditions: pesticide concentration, 100.0 ng/L; extraction temperature, 50 ℃; extraction time, 40 min; stirring rate, 500 r/min; desorption temperature, 280 ℃; desorption time, 5 min.

图2 UiO-66/HOCN复合材料的(a)TEM、(b)XRD、(c)等温氮气吸附-脱附以及(d)孔径分布表征图

Fig. 2 (a) Transmission electron microscopy (TEM) image, (b) X-ray diffraction (XRD) pattern, (c) N2 adsorption-desorption isotherms, and (d) pore size distribution of UiO-66/HOCN composite materials

图3 UiO-66/HOCN复合材料的(a)热稳定性表征图和(b)化学稳定性表征图

Fig. 3 (a) Thermal stability and (b) chemical stability of UiO-66/HOCN composite materials

图4 (a) 萃取温度、(b)萃取时间和(c)搅拌速率对9种农药萃取效率的影响(n=3)

Fig. 4 Effects of (a) extraction temperature, (b) extraction time and (c) agitation speed on extraction efficiency of the nine pesticides (n=3) Experimental conditions were the same as those in Fig. 1. When one of the factors was investigated, all other factors remain the same.

图5 (a) 解吸温度和(b)解吸时间对9种农药萃取效率的影响(n=3)

Fig. 5 Effects of (a) desorption temperature and (b) desorption time on extraction efficiency of the nine pesticides (n=3) Experimental conditions were the same as those in Fig. 1. When one of the factors was investigated, all other factors remain the same.

表2 所建立方法的线性范围、相关系数、检出限以及精密度

Table 2 Linear ranges, correlation coefficients (R), limits of detection (LODs), and precision of the proposed method

Compound	Linear range/(ng/L)	R	LOD/(ng/L)	RSDs/% (n=3)
				Single fiber		Fibers of batch-to-batch
				Intra-day	Inter-day	Fibers of batch-to-batch
Heptachlor	0.3-300.0	0.9996	0.1	4.9	6.8	7.2
Aldrin	0.3-500.0	0.9997	0.1	4.5	4.5	6.2
Heptachlor epoxide	0.3-300.0	0.9989	0.1	7.5	8.9	9.0
α-Chlordane	0.5-300.0	0.9986	0.3	5.1	7.9	9.2
p, p′-DDE	0.3-500.0	0.9978	0.1	4.5	8.2	8.3
α-Endosulfan	0.3-800.0	0.9999	0.1	4.2	4.7	5.2
p, p′-DDD	0.1-300.0	0.9999	0.03	4.3	6.4	7.8
p, p′-DDT	0.1-300.0	0.9999	0.03	5.4	6.5	8.4
Bifenthrin	0.8-500.0	0.9990	0.3	3.3	7.4	9.7

表3 本文方法与其他已报道方法的比较

Table 3 Comparison of the proposed method with other reported methods

Coating material	Linear range/(μg/L)	R	LODs/(ng/L)	RSDs/%	Ref.
PDMS: polydimethylsiloxane; DVB: divinylbenzene; CAR: carboxen; PEG: polyethylene glycol.
UiO-66/HOCN	0.1×10^-3-0.8	0.9978-0.9999	0.03-0.30	3.3-9.7	this study
ZnO/g-C₃N₄	0.3×10^-2-5.0	0.9981-0.9993	1.0-2.5	2.3-11.3	[9]
PDMS	0.1-500	0.9906-0.9988	40-410	3.2-11.3	[10]
PDMS/DVB	0.5-100	0.9901-0.9999	3-560	＜15	[11]
DVB/CAR/PDMS	1-100	0.9755-0.9997	200-400	7.2-24.6	[12]
PEG	-	0.9930-0.9990	3-145	4.2-10.0	[13]

表4 9种农药在实际红茶样品中的加标回收率及精密度(n=3)

Table 4 Recoveries and RSDs of the nine pesticides spiked in a black tea sample (n=3)

Compound	Background/(ng/L)(RSD/%)	Recoveries (RSDs) at three spiked levels/%
Compound	Background/(ng/L)(RSD/%)	8 ng/L	30 ng/L	100 ng/L
* Not detected.
Heptachlor	n. d.^*	82.9 (6.1)	87.5 (3.6)	94.9 (4.9)
Aldrin	6.6 (5.7)	92.9 (7.6)	98.1 (5.2)	98.8 (7.8)
Heptachlor epoxide	n. d.^*	111.2 (5.2)	109.5 (8.5)	87.4 (7.5)
α-Chlordane	n. d.^*	103.4 (2.5)	100.3 (4.3)	97.6 (6.3)
p, p′-DDE	n. d.^*	90.2 (7.1)	94.3 (5.6)	99.5 (4.3)
α-Endosulfan	54.7 (6.3)	93.2 (4.1)	98.5 (4.2)	111.0 (3.7)
p, p′-DDD	n. d.^*	85.5 (3.5)	89.4 (7.3)	105.0 (8.9)
p, p′-DDT	n. d.^*	92.4 (4.0)	90.2 (3.9)	106.0 (6.4)
Bifenthrin	185.8 (2.5)	102.8 (3.5)	106.1 (4.7)	117.0 (4.7)

图6 实际红茶样品和加标红茶样品的色谱图

Fig. 6 Chromatograms of a black tea sample and a black tea sample spiked with standards Experimental conditions were the same as those in Fig. 1. Spiked level: 30 ng/L of each of the nine pesticides. Peak identifications: 1. heptachlor; 2. aldrin; 3. heptachlor epoxide; 4. α-chlordane; 5. p, p′-DDE; 6. α-endosulfan; 7. p, p′-DDD; 8. p, p′-DDT; 9. bifenthrin.

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